Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from...Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.L...Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.展开更多
The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
Aqueous zinc metal batteries(AZMBs)are promising candidates for renewable energy storage,yet their practical deployment in subzero environments remains challenging due to electrolyte freezing and dendritic growth.Alth...Aqueous zinc metal batteries(AZMBs)are promising candidates for renewable energy storage,yet their practical deployment in subzero environments remains challenging due to electrolyte freezing and dendritic growth.Although organic additives can enhance the antifreeze properties of electrolytes,their weak polarity diminishes ionic conductivity,and their flammability poses safety concerns,undermining the inherent advantages of aqueous systems.Herein,we present a cost-effective and highly stable Na_(2)SO_(4)additive introduced into a Zn(ClO_(4))2-based electrolyte to create an organic-free antifreeze electrolyte.Through Raman spectroscopy,in situ optical microscopy,densityfunctional theory computations,and molecular dynamics simulations,we demonstrate that Na+ions improve low-temperature electrolyte performance and mitigate dendrite formation by regulating uniform Zn^(2+)deposition through preferential adsorption and electrostatic interactions.As a result,the Zn||Zn cells using this electrolyte achieve a remarkable cycling life of 360 h at-40℃ with 61% depth of discharge,and the Zn||PANI cells retained an ultrahigh capacity retention of 91%even after 8000 charge/discharge cycles at-40℃.This work proposes a cost-effective and practical approach for enhancing the long-term operational stability of AZMBs in low-temperature environments.展开更多
The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and fla...The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.展开更多
实验以废弃小麦秸秆为原料,基于KOH活化-高温烧结法制备了多孔碳材料,采用扫描电子显微镜(SEM)、N_(2)吸附/脱附测试和拉曼光谱(Raman)等测试方法,表征了材料的结构及形貌,并结合恒流充放电(GCD)和循环伏安(CV)测试技术,探究了其在锂离...实验以废弃小麦秸秆为原料,基于KOH活化-高温烧结法制备了多孔碳材料,采用扫描电子显微镜(SEM)、N_(2)吸附/脱附测试和拉曼光谱(Raman)等测试方法,表征了材料的结构及形貌,并结合恒流充放电(GCD)和循环伏安(CV)测试技术,探究了其在锂离子电池中的应用。实验结果表明,采用10 mol·L^(-1)KOH活化的碳材料所制备的电极在循环100次后,依然能具有348.4 m Ah·g^(-1)的比容量,且当电流密度增加到3.5 A·g^(-1)时,其比容量高达431.2 m Ah·g^(-1),表现出较高的倍率性能,这主要是由于材料较多的微孔空隙和较高的无序度,提供了更多的电化学活性点。展开更多
A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and...A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.展开更多
基金supported by the financial support from the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金financially supported by Shenzhen Science and Technology Program(JCYJ20240813142900001)Guangdong Provincial Key Laboratory of New Energy Materials Service Safety。
文摘Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
基金financially supported by the National Natural Science Foundation of China(Grant No.52377206,52307237)Natural Science Foundation of Heilongjiang Province of China(YQ2024E046)Postdoctoral Science Foundation of Heilongjiang Province of China(LBH-TZ2413,LBH-Z23198)。
文摘Aqueous zinc metal batteries(AZMBs)are promising candidates for renewable energy storage,yet their practical deployment in subzero environments remains challenging due to electrolyte freezing and dendritic growth.Although organic additives can enhance the antifreeze properties of electrolytes,their weak polarity diminishes ionic conductivity,and their flammability poses safety concerns,undermining the inherent advantages of aqueous systems.Herein,we present a cost-effective and highly stable Na_(2)SO_(4)additive introduced into a Zn(ClO_(4))2-based electrolyte to create an organic-free antifreeze electrolyte.Through Raman spectroscopy,in situ optical microscopy,densityfunctional theory computations,and molecular dynamics simulations,we demonstrate that Na+ions improve low-temperature electrolyte performance and mitigate dendrite formation by regulating uniform Zn^(2+)deposition through preferential adsorption and electrostatic interactions.As a result,the Zn||Zn cells using this electrolyte achieve a remarkable cycling life of 360 h at-40℃ with 61% depth of discharge,and the Zn||PANI cells retained an ultrahigh capacity retention of 91%even after 8000 charge/discharge cycles at-40℃.This work proposes a cost-effective and practical approach for enhancing the long-term operational stability of AZMBs in low-temperature environments.
基金supported by the National Natural Science Foundation of China(32501592,32271814,32301530,32471806)Young Elite Scientist Sponsorship Program by Cast(No.YESS20230242)+3 种基金Natural Science Foundation of Tianjin(23JCZDJC00630,24JCZDJC00630)the China Postdoctoral Science Foundation(2023M740563)Tianjin Enterprise Technology Commissioner Project(25YDTPJC00690)China Scholarship Council(202408120091,202408120105).
文摘The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.
文摘实验以废弃小麦秸秆为原料,基于KOH活化-高温烧结法制备了多孔碳材料,采用扫描电子显微镜(SEM)、N_(2)吸附/脱附测试和拉曼光谱(Raman)等测试方法,表征了材料的结构及形貌,并结合恒流充放电(GCD)和循环伏安(CV)测试技术,探究了其在锂离子电池中的应用。实验结果表明,采用10 mol·L^(-1)KOH活化的碳材料所制备的电极在循环100次后,依然能具有348.4 m Ah·g^(-1)的比容量,且当电流密度增加到3.5 A·g^(-1)时,其比容量高达431.2 m Ah·g^(-1),表现出较高的倍率性能,这主要是由于材料较多的微孔空隙和较高的无序度,提供了更多的电化学活性点。
文摘A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
